CN112899495A - Method for efficiently and deeply removing arsenic and antimony in crude copper from anode furnace - Google Patents

Abstract

The invention provides a method for efficiently and deeply removing arsenic and antimony in blister copper from an anode furnace, which comprises the following process steps: a, adding lead copper matte and copper miscellaneous ore into a side-blown converter for reduction smelting to produce copper matte; b, putting the matte into a converter for refining to produce crude copper; c, putting the raw copper into an anode furnace, and spraying alkaline flux into a molten pool by using a nitrogen injection technology to realize efficient and deep removal of arsenic and antimony in the raw copper to produce a copper anode plate; d, producing the electrolytic copper product by the copper anode plate through an electrolysis process flow. The invention adopts the alkaline flux which is prepared by the mixture of the soda ash and the lime in the anode furnace to directly spray the prepared alkaline flux into the molten pool under the injection of the nitrogen, thereby effectively solving the problem of low utilization rate of auxiliary materials which are directly added into the liquid level of the molten pool, achieving the aim of quickly and efficiently removing arsenic and antimony in the blister copper, and solving the problems of long production period, unstable index control, serious influence on the flow production capacity and the like of the traditional process.

Description

Method for efficiently and deeply removing arsenic and antimony in crude copper from anode furnace

Technical Field

The invention belongs to the technical field of pyrometallurgical processes, and particularly relates to a method for efficiently and deeply removing arsenic and antimony in blister copper from an anode furnace.

Background

The lead copper matte is an intermediate product in the electrolytic lead production process, mainly takes enriched copper element as a main component, and is also a raw material for recovering and producing electrolytic copper. Wherein, because lead copper matte contains a certain amount of arsenic and antimony elements, and needs to be removed in a side-blown furnace, a bottom-blown furnace or a converter, when the arsenic and antimony elements reach 0.05 percent, the removal of the impurities is regarded as the end point, slag can be discharged, a copper anode plate can be cast for producing electrolytic copper products in an electrolysis process, therefore, the removal efficiency and index control condition of the arsenic and antimony elements are a major factor restricting the production capacity, most of the prior domestic operations are to remove the arsenic and antimony in the blister copper by adding soda or lime in the converter process, a small part of enterprises add soda or lime in the anode furnace to remove the arsenic and antimony, the adding modes are that the soda or lime is directly added on the surface of a molten solution, the soda or the lime cannot be fully contacted with and reacted with the arsenic and antimony in the blister copper alloy, the soda or the lime floats on the surface of the blister copper molten pool due to the specific gravity being smaller than the blister copper after the direct melting, the utilization rate of, meanwhile, the utilization of one auxiliary material (soda ash or lime) has the problems of unsatisfactory arsenic and antimony removal effect, low efficiency, long period and the like.

Disclosure of Invention

The invention provides a method for efficiently and deeply removing arsenic and antimony in blister copper from an anode furnace in order to solve the problems, effectively solves the problem of low utilization rate of auxiliary materials directly added into the liquid level of a molten pool, and can achieve the purpose of rapidly and efficiently removing arsenic and antimony in blister copper.

The technical scheme of the invention is realized as follows: a method for efficiently and deeply removing arsenic and antimony in blister copper from an anode furnace comprises the following steps:

a. the lead copper matte and the copper miscellaneous ore are fed into a side-blown converter for reduction smelting to produce copper matte;

b. putting the matte into a converter for refining, adding quartz for removing lead, enabling lead to enter slag in the form of lead silicate to realize separation from copper, discharging the matte when the copper content in the matte reaches 96.5%, arsenic is less than or equal to 0.1%, antimony is less than or equal to 0.1% and lead is less than or equal to 0.15%, and enabling the produced matte to enter an anode furnace for refining;

c. putting the raw copper into an anode furnace, adding quartz sand at the temperature of 1150 ℃ (1100-: 1, after oxidizing for 30 minutes, starting to sample to measure the lead content, and when the lead content is less than or equal to 0.09 and the surface of the sample is not sulfur-filled, completely discharging slag in the anode furnace to finish lead removal;

after lead removal is finished, alkaline flux is adopted to remove residual arsenic and antimony elements in the crude copper, the alkaline flux comprises soda ash and lime, the ratio of the soda ash to the lime is 3:1, the temperature is kept at 1150-plus-1180 ℃, the prepared alkaline flux (the ratio of the soda ash to the lime is 3: 1) is directly sprayed into a molten pool under the blowing of nitrogen with the pressure of 0.4Mpa, then the molten pool is further oxidized to the end point, sampling and self-testing are carried out, when the content of the arsenic and the content of the antimony are both less than 0.05 percent, slag can be discharged, and then reduction operation is carried out to produce a copper anode plate;

d. the copper anode plate produces an electrolytic copper product through an electrolysis process.

The invention can realize that the prepared alkaline flux is directly injected into the blister copper molten pool by controlling the pressure to be 0.4MPa by using nitrogen, thereby realizing the full contact and reaction of the alkaline flux and arsenic and antimony in the blister copper, and solving the problem that the alkaline flux is directly added on the upper surface of the blister copper molten pool, and the arsenic and antimony in the blister copper can not be effectively removed because the specific gravity of the alkaline flux is less than that of the blister copper after the alkaline flux is directly floated on the surface of the molten pool and the arsenic and antimony in the blister copper can not be effectively removed because the alkaline flux can not be fully contacted and reacted with. Therefore, compared with the traditional process, the method can quickly and efficiently remove the arsenic and antimony elements in the blister copper.

The invention has the beneficial effects that:

the invention adopts the alkaline flux which is prepared by the mixture of the soda ash and the lime in the anode furnace to directly spray the prepared alkaline flux into the molten pool under the injection of the nitrogen, thereby effectively solving the problem of low utilization rate of auxiliary materials which are directly added into the liquid level of the molten pool, achieving the aim of quickly and efficiently removing arsenic and antimony in the blister copper, and solving the problems of long production period, unstable index control, serious influence on the flow production capacity and the like of the traditional process. The process is simple and easy to control, the operation cost is low, and the generated benefit is high.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

For a better understanding and implementation, a method for removing arsenic and antimony from blister copper in an anode furnace is described in detail below:

example 1:

the method comprises the following steps:

a. the lead copper matte and the copper miscellaneous ore are fed into a side-blown converter for reduction smelting to produce copper matte;

b. putting the matte into a converter for refining, adding quartz for removing lead, enabling lead to enter slag in the form of lead silicate to realize separation from copper, discharging the matte when the copper content in the matte reaches 96.5%, arsenic is less than or equal to 0.1%, antimony is less than or equal to 0.1% and lead is less than or equal to 0.15%, and enabling the produced matte to enter an anode furnace for refining;

c. putting the blister copper into an anode furnace for 180 tons at 1150 ℃, adding quartz sand, oxidizing to remove lead, adding 500 kg of quartz stone when the lead content is 0.15%, oxidizing the air quantity of a unilateral oxidation pipe for 500 Nm/h, oxidizing both sides simultaneously, sampling after 30 minutes, completely discharging the slag in the anode furnace when the lead content is less than or equal to 0.09 and the surface of a sample is free of sulfur filling by using a spectrometer, removing residual arsenic and antimony in the blister copper by using an alkaline flux (the ratio of soda to lime is 3: 1), keeping the temperature at 1150 ℃, keeping the temperature in the whole impurity removal process to keep an ascending trend, driving 9.3 tons of the alkaline flux into a melt by using nitrogen (the pressure is 0.4 MPa), then further oxidizing to the end point, respectively adding 7 tons of soda and lime when the content is As0.8 and Sb0.4, and discharging the slag when the arsenic and antimony content are less than 0.05% by using the spectrometer, the time for removing arsenic and antimony in the crude copper is 8-12h, and then the crude copper is subjected to reduction operation to produce a copper anode plate.

Experimental data:

1. the composition of the blister copper is shown in the specification

Name (R)	As	Sb
			Blister copper	0.8	0.4

2. Arsenic and antimony removal by alkaline flux blowing 8h sampling assay data table%

Name (R)	As	Sb
			Blister copper	0.033	0.042

Comparative example 2:

the prior art adopts the following steps:

a. the lead copper matte and the copper miscellaneous ore are fed into a side-blown converter for reduction smelting to produce copper matte;

b. putting copper matte into a converter for refining, adding quartz for removing lead, enabling lead to enter slag in the form of lead silicate to be separated from copper, starting to add soda ash to remove arsenic and antimony in the blister copper when the copper content in the blister copper reaches 96.5%, specifically, operating by traveling crane for hoisting, adding the soda ash into the converter through a chute, pouring out alkali liquor through a rotary converter after the soda ash is melted into liquid and does not react any more, then adding the soda ash, repeating the above operations until the arsenic and antimony contents in the blister copper are respectively less than 0.05% or less, and enabling the arsenic and antimony to be removed for 18-24 hours, and then, entering an anode furnace for refining;

c. putting the blister copper into an anode furnace for 180 tons, heating to 1150 ℃, adding quartz sand, oxidizing to remove lead, adding 500 kg of quartz stone when the lead content is 0.15%, carrying out oxidation on one side of an oxidation pipe with the oxidation air volume of 500 Nm/h, simultaneously oxidizing the two sides of the oxidation pipe, after oxidizing for 30 minutes, sampling by using a spectrometer, and after the lead content is less than or equal to 0.09 and the surface of a sample has no sulfur filling phenomenon, completely discharging slag in the anode furnace, and then carrying out reduction operation to produce a copper anode plate.

Experimental data:

1. the composition of the blister copper is shown in the specification

Name (R)	As	Sb
			Blister copper	0.65	0.38

2. Adding soda ash into a converter to remove arsenic and antimony for 19h, and sampling and testing data table%

Name (R)	As	Sb
			Blister copper	0.048	0.039

The comparison of the two groups of cases shows that the self-made alkaline flux is selected to remove arsenic and antimony in the blister copper in the anode furnace by adopting the blowing technology, and the removal by adding soda ash in the converter in the traditional process has the advantages of short impurity removal period, high production efficiency, more stable index control and the like.

Claims (1)

1. A method for efficiently and deeply removing arsenic and antimony in blister copper from an anode furnace is characterized by comprising the following steps:

a. the lead copper matte and the copper miscellaneous ore are fed into a side-blown converter for reduction smelting to produce copper matte;

b. putting the matte into a converter for refining, adding quartz for removing lead, enabling lead to enter slag in the form of lead silicate to realize separation from copper, discharging the matte when the copper content in the matte reaches 96.5%, arsenic is less than or equal to 0.1%, antimony is less than or equal to 0.1% and lead is less than or equal to 0.15%, and enabling the produced matte to enter an anode furnace for refining;

c. putting the raw copper into an anode furnace, adding quartz sand at the temperature of 1150 ℃ (1100-: 1, after oxidizing for 30 minutes, starting to sample to measure the lead content, and when the lead content is less than or equal to 0.09 and the surface of the sample is not sulfur-filled, completely discharging slag in the anode furnace to finish lead removal;

after lead removal is finished, alkaline flux is adopted to remove residual arsenic and antimony elements in the crude copper, the alkaline flux comprises soda ash and lime, the ratio of the soda ash to the lime is 3:1, the temperature is kept at 1150-plus-1180 ℃, the prepared alkaline flux is directly sprayed into a molten pool under the blowing of nitrogen with the pressure of 0.4Mpa, the ratio of the soda ash to the lime in the alkaline flux is 3:1, the mixture is further oxidized to the end point, sampling and self-testing are carried out, when the content of arsenic and antimony is less than 0.05 percent, slag can be discharged, and then a copper anode plate is produced after reduction operation;

d. the copper anode plate produces an electrolytic copper product through an electrolysis process.

Images